Triphenylene-based materials for organic electroluminescent devices

ABSTRACT

The present invention relates to compounds of the formula (1) and (2) which are suitable for use in electronic devices, in particular organic electroluminescent devices.

The present invention relates to materials for use in electronicdevices, in particular in organic electroluminescent devices.

The structure of organic electroluminescent devices (OLEDs) in whichorganic semiconductors are employed as functional materials isdescribed, for example, in U.S. Pat. No. 4,539,507, U.S. Pat. No.5,151,629, EP 0676461 and WO 98/27136. The emitting materials employedhere are increasingly organometallic complexes which exhibitphosphorescence instead of fluorescence (M. A. Baldo et al., Appl. Phys.Lett. 1999, 75, 4-6). For quantummechanical reasons, an up to four-foldenergy and power efficiency is possible using organometallic compoundsas phosphorescent emitters. In general, there is still a need forimprovement, for example with respect to efficiency, operating voltageand lifetime, in the case of OLEDs, in particular also in the case ofOLEDs which exhibit triplet emission (phosphorescence). This applies, inparticular, to OLEDs which emit in the relatively short-wave region, forexample green.

The properties of phosphorescent OLEDs are determined not only by thetriplet emitters employed. In particular, the other materials used, suchas matrix materials, hole-blocking materials, electron-transportmaterials, hole-transport materials and electron- or exciton-blockingmaterials, are also of particular importance here. Improvements in thesematerials can thus also result in significant improvements in the OLEDproperties. There is also still a need for improvement in the case ofthese materials for fluorescent OLEDs.

In accordance with the prior art, triphenylene derivatives are used asmatrix materials for phosphorescent emitters, for example in accordancewith JP 2005/071983 or WO 2006/038709. However, there is also a need forimprovement on use of these matrix materials, in particular with respectto the efficiency and lifetime of the device.

The object of the present invention is the provision of compounds whichare suitable for use in a fluorescent or phosphorescent OLED, inparticular a phosphorescent OLED, for example as matrix material and/oras holetransport/electron-blocking material or exciton-blocking materialand/or as electron-transport or hole-blocking material. In particular,it is the object of the present invention to provide matrix materialswhich are suitable for green- and red-phosphorescent OLEDs.

Surprisingly, it has been found that triphenylene derivatives which aresubstituted in positions 1 and 12 by aromatic or heteroaromatic ringsystems, carbonyl groups or phosphine oxide groups or in which positions1 and 12 are bridged by a group selected from in each case optionallysubstituted boron, carbon, silicon, germanium, tin, nitrogen, oxygen,sulfur or phosphorus achieve this object and result in improvements inthe organic electroluminescent device, in particular with respect to thelifetime, efficiency and operating voltage. This applies, in particular,to red- and green-phosphorescent electroluminescent devices, especiallyon use of the compounds according to the invention as matrix material.The materials according to the invention can be synthesised in few stepsand in high yield. The present invention therefore relates to thesematerials and to organic electroluminescent devices which comprisecompounds of this type.

For clarity, the numbering of triphenylene is depicted below:

The present invention therefore relates to a neutral compound of thefollowing formula (1) or formula (2),

where the following applies to the symbols and indices used:

-   X is on each occurrence, identically or differently, preferably    identically, BR², C(R²)₂, C═O, Si(R²)₂, Ge(R²)₂, Sn(R²)₂, NR², O, S,    SO, SO₂, PR² or P(═O)R²,    -   or X is, for n=0, a group of the following formula (3),

-   A is C, Si, Ge or Sn; the dashed bonds on A here indicate the    bonding to the triphenylene;-   Y is BR², O, S, NR², PR² or P(═O)R²;-   Z is on each occurrence, identically or differently, CR¹ or N, with    the proviso that a maximum of two groups Z per ring stand for N;-   R is selected on each occurrence, identically or differently, from    the group consisting of N(Ar¹)₂, C(═O)Ar¹, P(═O)(Ar¹)₂ and an    aromatic or heteroaromatic ring system having 5 to 60 aromatic ring    atoms, which may in each case be substituted by one or more radicals    R¹;-   Ar¹ is on each occurrence, identically or differently, an aromatic    or heteroaromatic ring system having 5 to 60 aromatic ring atoms,    which may be substituted by one or more non-aromatic radicals R³;    two radicals Ar¹ here which are bonded to the same N atom or P atom    may also be bridged to one another by a single bond or a bridge    selected from N(R⁴), C(R⁴)₂, O or S,-   R¹ is selected on each occurrence, identically or differently, from    the group consisting of H, D, F, Cl, Br, I, CN, NO₂, N(Ar¹)₂,    N(R³)₂, C(═O)Ar¹, C(═O)R³, P(═O)(Ar¹)₂, a straight-chain alkyl,    alkoxy or thioalkyl group having 1 to 40 C atoms or a branched or    cyclic alkyl, alkoxy or thioalkyl group having 3 to 40 C atoms or an    alkenyl or alkynyl group having 2 to 40 C atoms, where the alkyl,    alkoxy, thioalkoxy, alkenyl or alkynyl group may in each case be    substituted by one or more radicals R³ and where one or more    non-adjacent CH₂ groups may be replaced by R³C═CR³, C≡C, Si(R³)₂,    Ge(R³)₂, Sn(R³)₂, C═O, C═S, C═Se, C═NR³, P(═O)(R³), SO, SO₂, NR³, O,    S or CONR³ and where one or more H atoms may be replaced by D, F,    Cl, Br, I, CN or NO₂, an aromatic or heteroaromatic ring system    having 5 to 60 aromatic ring atoms, which may in each case be    substituted by one or more radicals R³, an aryloxy or heteroaryloxy    group having 5 to 60 aromatic ring atoms, which may be substituted    by one or more radicals R³, or a combination of these systems, where    two or more adjacent substituents R¹ which are bonded to the same    benzene ring may optionally form a monocyclic or polycyclic,    aliphatic, aromatic or heteroaromatic ring system;-   R² is selected on each occurrence, identically or differently, from    the group consisting of a straight-chain alkyl group having 1 to 20    C atoms or a branched or cyclic alkyl group having 3 to 20 C atoms,    each of which may be substituted by one or more radicals R³, where    one or more non-adjacent CH₂ groups may be replaced by R³C═CR³, C≡C,    Si(R³)₂, C═O, C═NR³, P(═O)(R³), SO, SO₂, NR³, O, S or CONR³ and    where one or more H atoms may be replaced by D, F, Cl, Br, I, CN or    NO₂, or an aromatic or heteroaromatic ring system having 5 to 60    aromatic ring atoms, which may in each case be substituted by one or    more radicals R³, where two substituents R² which are bonded to the    same carbon, silicon, germanium or tin atom may optionally form a    monocyclic or polycyclic, aliphatic, aromatic or heteroaromatic ring    system with one another, which may be substituted by one or more    radicals R³;-   R³ is selected on each occurrence, identically or differently, from    the group consisting of H, D, F, Cl, Br, I, CN, NO₂, N(R⁴)₂,    C(═O)Ar¹, C(═O)R⁴, P(═O)(Ar¹)₂, a straight-chain alkyl, alkoxy or    thioalkyl group having 1 to 40 C atoms or a branched or cyclic    alkyl, alkoxy or thioalkyl group having 3 to 40 C atoms or an    alkenyl or alkynyl group having 2 to 40 C atoms, where the alkyl,    alkoxy, thioalkyl, alkenyl or alkynyl group may be substituted by    one or more radicals R⁴ and where one or more non-adjacent CH₂    groups may be replaced by R⁴C═CR⁴, C≡C, Si(R⁴)₂, C═O, C═NR⁴,    P(═O)(R⁴), SO, SO₂, NR⁴, O, S or CONR⁴ and where one or more H atoms    may be replaced by D, F, Cl, Br, I, CN or NO₂, an aromatic or    heteroaromatic ring system having 5 to 60 aromatic ring atoms, which    may in each case be substituted by one or more radicals R⁴, an    aryloxy or heteroaryloxy group having 5 to 60 aromatic ring atoms,    which may be substituted by one or more radicals R⁴, or a    combination of these systems, where two or more adjacent    substituents R³ may optionally form a monocyclic or polycyclic,    aliphatic, aromatic or heteroaromatic ring system, which may be    substituted by one or more radicals R⁴;-   R⁴ is selected from the group consisting of H, D, F, CN, an    aliphatic hydrocarbon radical having 1 to 20 C atoms, an aromatic or    heteroaromatic ring system having 5 to 30 aromatic ring atoms, in    which one or more H atoms may be replaced by D, F, Cl, Br, I, CN or    an alkyl group having 1 to 5-C atoms, where two or more adjacent    substituents R⁴ may form a mono- or polycyclic, aliphatic, aromatic    or heteroaromatic ring system with one another;-   n is 0 or 1;    with the proviso that at least one group R¹ in formula (1) stands    for an aromatic or heteroaromatic ring system if X stands for C═O,    O, S, SO or SO₂ and n=0;    and furthermore with the proviso that the following compounds are    excluded from the invention:

A “non-aromatic radical” R³, as mentioned in the definition of Ar¹, is aradical in accordance with the definition of R³ which contains noaromatic or heteroaromatic groups, i.e., for example, also no aromaticcarbonyl group.

An aryl group in the sense of this invention contains 6 to 60 C atoms; aheteroaryl group in the sense of this invention contains 2 to 60 C atomsand at least one heteroatom, with the proviso that the sum of C atomsand heteroatoms is at least 5. The heteroatoms are preferably selectedfrom N, O and/or S. An aryl group or heteroaryl group here is taken tomean either a simple aromatic ring, i.e. benzene, or a simpleheteroaromatic ring, for example pyridine, pyrimidine, thiophene, etc.,or a condensed (anellated) aryl or heteroaryl group, for examplenaphthalene, anthracene, phenanthrene, quinoline, isoquinoline, etc.Aromatic groups which are linked to one another by a single bond, suchas, for example, biphenyl or bipyridine, are, by contrast, not referredto as aryl or heteroaryl group, but instead as aromatic ring system.

An aromatic ring system in the sense of this invention contains 6 to 60C atoms in the ring system. A heteroaromatic ring system in the sense ofthis invention contains 2 to 60 C atoms and at least one heteroatom inthe ring system, with the proviso that the sum of C atoms andheteroatoms is at least 5. The heteroatoms are preferably selected fromN, O and/or S. For the purposes of this invention, an aromatic orheteroaromatic ring system is intended to be taken to mean a systemwhich does not necessarily contain only aryl or heteroaryl groups, butinstead in which, in addition, a plurality of aryl or heteroaryl groupsmay be connected by a non-aromatic unit (preferably less than 10% of theatoms other than H), such as, for example, a C, N, O or Si atom. Thus,for example, systems such as fluorene, 9,9′-spirobifluorene,9,9-diarylfluorene, triarylamine, diaryl ether, stilbene, etc., are alsointended to be taken to be aromatic ring systems for the purposes ofthis invention, as are systems in which two or more aryl groups areconnected, for example, by an alkyl group having one to five C atoms ora carbonyl group.

For the purposes of the present invention, an aliphatic hydrocarbonradical or an alkyl group or an alkenyl or alkynyl group, which maytypically contain 1 to 40 or also 1 to 20 C atoms and in which, inaddition, individual H atoms or CH₂ groups may be substituted by theabove-mentioned groups, is preferably taken to mean the radicals methyl,ethyl, n-propyl, i-propyl, n-butyl, i-butyl, s-butyl, t-butyl,2-methylbutyl, n-pentyl, s-pentyl, neopentyl, cyclopentyl, n-hexyl,neohexyl, cyclohexyl, n-heptyl, cycloheptyl, n-octyl, cyclooctyl,2-ethylhexyl, trifluoromethyl, pentafluoroethyl, 2,2,2-trifluoroethyl,ethenyl, propenyl, butenyl, pentenyl, cyclopentenyl, hexenyl,cyclohexenyl, heptenyl, cycloheptenyl, octenyl, cyclooctenyl, ethynyl,propynyl, butynyl, pentynyl, hexynyl, heptynyl or octynyl. An alkoxygroup having 1 to 40 C atoms is preferably taken to mean methoxy,trifluoromethoxy, ethoxy, n-propoxy, i-propoxy, n-butoxy, i-butoxy,s-butoxy, t-butoxy, n-pentoxy, s-pentoxy, 2-methylbutoxy, n-hexoxy,cyclohexyloxy, n-heptoxy, cycloheptyloxy, n-octyloxy, cyclooctyloxy,2-ethylhexyloxy, pentafluoroethoxy and 2,2,2-trifluoroethoxy. Athioalkyl group having 1 to 40 C atoms is taken to mean, in particular,methylthio, ethylthio, n-propylthio, i-propylthio, n-butylthio,i-butylthio, s-butylthio, t-butylthio, n-pentylthio, s-pentylthio,n-hexylthio, cyclohexylthio, n-heptylthio, cycloheptylthio, n-octylthio,cyclooctylthio, 2-ethylhexylthio, trifluoromethylthio,pentafluoroethylthio, 2,2,2-trifluoroethylthio, ethenylthio,propenylthio, butenylthio, pentenylthio, cyclopentenylthio, hexenylthio,cyclohexenylthio, heptynylthio, cycloheptenylthio, octenylthio,cyclooctenylthio, ethynylthio, propynylthio, butynylthio, pentynylthio,hexynylthio, heptynylthio or octynylthio. In general, alkyl, alkoxy orthioalkyl groups in accordance with the present invention may bestraight-chain, branched or cyclic, where one or more non-adjacent CH₂groups may be replaced by the above-mentioned groups; furthermore, oneor more H atoms may also be replaced by D, F, Cl, Br, I, CN or NO₂,preferably F, Cl or CN, further preferably F or CN, particularlypreferably CN.

An aromatic or heteroaromatic ring system having 5 to 60 aromatic ringatoms, which may also in each case be substituted by the above-mentionedradicals R² or a hydrocarbon radical and which may be linked via anydesired positions on the aromatic or heteroaromatic ring system, istaken to mean, in particular, groups derived from benzene, naphthalene,anthracene, benzanthracene, phenanthrene, pyrene, chrysene, perylene,fluoranthene, naphthacene, pentacene, benzopyrene, biphenyl,biphenylene, terphenyl, triphenylene, fluorene, spirobifluorene,dihydrophenanthrene, dihydropyrene, tetrahydropyrene, cis- ortrans-indenofluorene, cis- or trans-indenocarbazole, cis- ortrans-indolocarbazole, truxene, isotruxene, spirotruxene,spiroisotruxene, furan, benzofuran, isobenzofuran, dibenzofuran,thiophene, benzothiophene, isobenzothiophene, dibenzothiophene, pyrrole,indole, isoindole, carbazole, pyridine, quinoline, isoquinoline,acridine, phenanthridine, benzo-5,6-quinoline, benzo-6,7-quinoline,benzo-7,8-quinoline, phenothiazine, phenoxazine, pyrazole, indazole,imidazole, benzimidazole, naphthimidazole, phenanthrimidazole,pyridimidazole, pyrazinimidazole, quinoxalinimidazole, oxazole,benzoxazole, naphthoxazole, anthroxazole, phenanthroxazole, isoxazole,1,2-thiazole, 1,3-thiazole, benzothiazole, pyridazine,hexaazatriphenylene, benzopyridazine, pyrimidine, benzopyrimidine,quinoxaline, 1,5-diazaanthracene, 2,7-diazapyrene, 2,3-diazapyrene,1,6-diazapyrene, 1,8-diazapyrene, 4,5-diazapyrene,4,5,9,10-tetraazaperylene, pyrazine, phenazine, phenoxazine,phenothiazine, fluorubin, naphthyridine, azacarbazole, benzocarboline,phenanthroline, 1,2,3-triazole, 1,2,4-triazole, benzotriazole,1,2,3-oxadiazole, 1,2,4-oxadiazole, 1,2,5-oxadiazole, 1,3,4-oxadiazole,1,2,3-thiadiazole, 1,2,4-thiadiazole, 1,2,5-thiadiazole,1,3,4-thiadiazole, 1,3,5-triazine, 1,2,4-triazine, 1,2,3-triazine,tetrazole, 1,2,4,5-tetrazine, 1,2,3,4-tetrazine, 1,2,3,5-tetrazine,purine, pteridine, indolizine and benzothiadiazole or groups derivedfrom combinations of these systems.

In a preferred embodiment of the invention, a maximum of one group Z perring stands for N and the other groups Z stand, identically ordifferently on each occurrence, for CR¹. In a particularly preferredembodiment of the invention, all groups Z stand, identically ordifferently on each occurrence, for CR¹.

Preferred embodiments of the compounds of the formula (1) and (2) aretherefore the compounds of the following formulae (4) to (7),

where the symbols used have the meanings given above. X in formula (4)and (6) cannot be a group of the formula (3).

Preferred embodiments of the compounds of the formulae (4) to (7) arethe compounds of the following formulae (4a) to (7a),

where the symbols used have the meanings given above.

In compounds of the formula (1) where n=0 or formula (4) or formula(4a), X is preferably selected from the group consisting of C(R²)₂,Si(R²)₂ and N(R²), particularly preferably N(R²).

R² preferably stands, identically or differently on each occurrence, foran aromatic or heteroaromatic ring system having 5 to 40 aromatic ringatoms, preferably having 5 to 24 aromatic ring atoms, which may in eachcase also be substituted by one or more radicals R³ and where tworadicals R² which are bonded to the same carbon, silicon, germanium ortin atom may also form an aromatic ring system with one another and maythus form a spiro system. Particularly preferred aromatic orheteroaromatic ring systems R² are shown below together with thepreferred groups for R¹.

In a preferred embodiment of the compounds of the formula (1) in which Xstands for a group of the formula (3), or formula (5) or formula (5a),the two triphenylene moieties which are bonded to A are in each casesubstituted identically. In these compounds, A furthermore preferablystands for carbon or silicon, particularly preferably for carbon.

In compounds of the formula (1) where n=1 or formula (6) or formula(6a), the group X—Y—X is preferably selected from the group consistingof C(R²)₂—O—C(R²)₂, Si(R²)₂—O—Si(R²)₂, O—BR²—O, O—PR²—O, O—P(═O)R²—O andC(═O)—NR²—C(═O).

In a preferred embodiment of the compounds of the formula (2) or formula(7) or formula (7a), the two radicals R are selected identically.

In a preferred embodiment of the invention, R¹ in the formulae givenabove is selected, identically or differently on each occurrence, fromthe group consisting of H, D, F, Cl, Br, CN, N(Ar¹)₂, C(═O)Ar¹, astraight-chain alkyl or alkoxy group having 1 to 10 C atoms or abranched or cyclic alkyl or alkoxy group having 3 to 10 C atoms or analkenyl or alkynyl group having 2 to 10 C atoms, each of which may besubstituted by one or more radicals R³, where one or more non-adjacentCH₂ groups may be replaced by 0 and where one or more H atoms may bereplaced by D or F, or an aromatic or heteroaromatic ring system having5 to 30 aromatic ring atoms, which may in each case be substituted byone or more radicals R³.

In a particularly preferred embodiment of the invention, R¹ in theformulae given above is selected, identically or differently on eachoccurrence, from the group consisting of H, D, F, CN, a straight-chainalkyl group having 1 to 10 C atoms or a branched or cyclic alkyl grouphaving 3 to 10 C atoms, each of which may be substituted by one or moreradicals R³, where one or more H atoms may be replaced by D or F, or anaromatic or heteroaromatic ring system having 5 to 18 aromatic ringatoms, which may in each case be substituted by one or more radicals R³.

In a further embodiment of the invention, the radicals R¹ which arebonded directly to the triphenylene are equal to H.

For compounds which are processed by vacuum evaporation, the alkylgroups preferably have not more than four C atoms, particularlypreferably not more than 1 C atom. For compounds which are processedfrom solution, compounds which are substituted by alkyl groups having upto 10 C atoms or which are substituted by oligoarylene groups, forexample ortho-, meta-, para- or branched terphenyl groups orquaterphenyl groups, are also suitable.

Depending on the use of the compounds according to the invention,different substituents R and R¹ are selected.

If the compounds of the formulae (1) or (2) or (4) to (7) or (4a) to(7a) are used as matrix material for phosphorescent emitters, at leastone radical R¹ preferably stands for N(Ar¹)₂, C(═O)Ar¹, P(═O)(Ar¹)₂ orfor an aromatic or heteroaromatic ring system having 5 to 60 aromaticring atoms, which may be substituted by one or more radicals R³, wherethe group Ar¹ or the radicals on Ar¹ or the aromatic or heteroaromaticring system or the radicals R³ on the aromatic or heteroaromatic ringsystem contain no condensed aryl groups having more than 10 C atoms andno condensed heteroaryl groups in which more than two aryl or 6-memberedheteroaryl groups are condensed directly onto one another.

In a particularly preferred embodiment of the invention, Ar¹ or theradicals on Ar¹ or the aromatic or heteroaromatic ring system or theradicals R³ on the aromatic or heteroaromatic ring system contain nocondensed aryl groups and no condensed heteroaryl groups in which two ormore aryl or 6-membered heteroaryl groups are condensed directly ontoone another.

Particularly preferred groups Ar¹ are selected from the group consistingof phenyl, ortho-, meta- or para-biphenyl, ortho-, meta- orpara-terphenyl, ortho-, meta-, para- or branched quaterphenyl, fluoreneor spirobifluorene, each of which may be substituted by one or morenon-aromatic radicals R³, but are preferably unsubstituted.

Particularly preferred aromatic ring systems R¹ and R² are selected fromthe group consisting of phenyl, ortho-, meta- or para-biphenyl, ortho-,meta- or para-terphenyl, ortho-, meta-, para- or branched quaterphenyl,fluorene or spirobifluorene, each of which may be substituted by one ormore radicals R³, but are preferably unsubstituted.

Particularly preferred heteroaromatic ring systems R¹ and R² contain, asheteroaryl group, triazine, pyrimidine, pyrazine, pyridazine, pyridine,benzothiophene, benzofuran, indole, carbazole, azacarbazole,diazacarbazole, dibenzothiophene and/or dibenzofuran. The heteroaromaticring systems here are, in particular, selected from the structures ofthe following formulae (8) to (38),

where R³ has the meanings given above and the dashed bond represents thebond to the triphenylene skeleton or to X.

Preferred embodiments of the groups of the formulae (8) to (38) are thestructures of the following formulae (8a) to (38a),

where R³ has the meanings given above and the dashed bond represents thebond to the triphenylene skeleton or to X. R³ in formula (8a) preferablystands, identically or differently, for an aromatic or heteroaromaticring system having 5 to 24 aromatic ring atoms, in particular,identically or differently, for phenyl, biphenyl, terphenyl orquaterphenyl.

If R¹ or R stands for a group N(Ar¹)₂, this group is then preferablyselected from the structures of the following formula (39) or (41), andif R¹ or R² or R stands for an aromatic or heteroaromatic ring systemwhich is a triarylamine or triheteroarylamine group, this group is thenpreferably selected from the structures of the following formula (40),

where the symbols used have the meanings given above, the dashed bondrepresents the bond to the triphenylene skeleton or in formula (40) alsoto X and furthermore:

-   Ar² is, identically or differently on each occurrence, an aromatic    or heteroaromatic ring system having 5 to 24 aromatic ring atoms,    which may be substituted by one or more radicals R³; the sum of the    aromatic ring atoms of all groups Ar² together is not greater than    60 here;-   E is selected from the group consisting of C(R⁴)₂, NR⁴, O or S.

Ar¹ in formula (39) and Ar² in formula (40) preferably stands,identically or differently on each occurrence, for phenyl, 1- or2-naphthyl, ortho-, meta- or para-biphenyl, ortho-, meta-, para- orbranched terphenyl, ortho-, meta-, para- or branched quaterphenyl,2-fluorenyl or 2-spirobifluorenyl, each of which may be substituted byone or more radicals R³.

If the compound of the formula (2) or (7) or (7a) is used as matrixmaterial for phosphorescent emitters, R furthermore preferably stands,identically or differently on each occurrence, for N(Ar¹)₂, C(═O)Ar¹,P(═O)(Ar¹)₂ or an aromatic or heteroaromatic ring system having 5 to 60aromatic ring atoms, which may be substituted by one or more radicalsR¹, where the group Ar¹ or the radicals on Ar¹ or the aromatic orheteroaromatic ring system or the radicals R¹ on the aromatic orheteroaromatic ring system contains no condensed aryl groups having morethan 10 C atoms and no condensed heteroaryl groups in which more thantwo aryl or 6-membered heteroaryl groups are condensed directly onto oneanother.

In a particularly preferred embodiment of the invention, Ar¹ or theradicals on Ar¹ or the aromatic or heteroaromatic ring system or theradicals R¹ on the aromatic or heteroaromatic ring system contain nocondensed aryl groups and no condensed heteroaryl groups in which two ormore aryl or 6-membered heteroaryl groups are condensed directly ontoone another.

Very particularly preferred groups Ar¹ are selected from the groupconsisting of phenyl, ortho-, meta- or para-biphenyl, ortho-, meta- orpara-terphenyl, ortho-, meta-, para- or branched quaterphenyl, fluoreneor spirobifluorene, each of which may be substituted by one or morenon-aromatic radicals R³, but is preferably unsubstituted.

Very particularly preferred aromatic or heteroaromatic ring systems R informula (2) are selected from the group consisting of phenyl, ortho-,meta- or para-biphenyl, ortho-, meta- or para-terphenyl, ortho-, meta-,para- or branched quaterphenyl, fluorene, spirobifluorene, triazine,pyridine, pyrazine, pyrimidine, pyridazine or carbazole, each of whichmay be substituted by one or more radicals R¹, but is preferablyunsubstituted.

If the compounds of the formulae (1) or (2) or (4) to (7) or (4a) to(7a) are used as matrix material for a fluorescent emitter, at least oneradical R¹ and/or at least one radical R² which is bonded to X and/or atleast one radical R in the formulae (2), (7) or (7a) preferably standsfor an aromatic or heteroaromatic ring system which contains at leastone aryl group having at least three condensed six-membered rings,preferably anthracene. X here preferably stands for N(R²) or for C(R²)₂.

If the compounds of the formulae (1) or (2) or (4) to (7) or (4a) to(7a) are used as fluorescent emitter, X preferably stands for N(R²) andR² stands for an aromatic or heteroaromatic ring system which containsat least one aryl group or an aromatic ring system having at least twocondensed six-membered rings, which is preferably bonded directly to thenitrogen of the group X. The condensed aryl group here is preferablyselected from anthracene, pyrene, phenanthrene, chrysene,monobenzoindenofluorene or dibenzoindenofluorene.

If the compounds of the formulae (1) or (2) or (4) to (7) or (4a) to(7a) are used as electron-transport material, at least one radical R¹and/or at least one radical R in the formulae (2), (7) or (7a)preferably stands for C(═O)Ar¹, P(═O)(Ar¹)₂ or for an electron-deficientheteroaromatic ring system having 5 to 40 aromatic ring atoms,preferably having 5 to 25 aromatic ring atoms, which may be substitutedby one or more radicals R³; and/or X in compounds of the formula (1)where n=0 preferably stands for BR², C═O, SO, SO₂ or P(═O)(R²)₂. Anelectron-deficient heteroaromatic ring system in the sense of thepresent invention is a heteroaromatic ring system which contains atleast one electron-deficient heteroaryl group, which is either a6-membered heteroaryl group having at least one nitrogen atom or a5-membered heteroaryl group having at least two heteroatoms.

Particularly preferred electron-deficient heteroaromatic ring systems R¹contain, as heteroaryl group, at least one group selected from triazine,pyrimidine, pyrazine, pyridazine, pyridine, imidazole, pyrazole,oxazole, oxadiazole, triazole, thiazole, thiadiazole, benzimidazole,quinoline, isoquinoline and quinoxaline. The heteroaromatic ring systemshere are, in particular, selected from the structures of the formulae(8) to (11) and (8a) to (11a) given above or from the following formulae(42) to (45),

where R³ has the meanings given above and the dashed bond represents thebond to the triphenylene skeleton.

Preferred embodiments of the groups of the formulae (42) to (45) are thestructures of the following formulae (42a) to (45a),

where R³ has the meanings given above and the dashed bond represents thebond to the triphenylene skeleton. R³ here preferably stands,identically or differently, for an aromatic or heteroaromatic ringsystem having 5 to 24 aromatic ring atoms, in particular, identically ordifferently, for phenyl, biphenyl, terphenyl or quaterphenyl.

If the compounds of the formulae (1) or (2) or (4) to (7) or (4a) to(7a) are used as hole-transport material or as emitting compound, atleast one radical R¹ and/or R preferably stands for N(Ar¹)₂, for atriarylamino group or for an electron-rich heteroaromatic ring systemhaving 5 to 40 aromatic ring atoms, in particular 5 to 25 aromatic ringatoms, which may be substituted by one or more radicals R³, inparticular for a radical of one of the formulae (39) to (41) givenabove; and/or X in compounds of the formula (1) where n=0 stands for NR²or PR². An electron-rich heteroaromatic ring system in the sense of thepresent invention is a heteroaromatic ring system which contains atleast one electron-rich heteroaryl group, which is a 5-memberedheteroaryl group having precisely one heteroatom, onto which, inaddition, one or more aryl groups may be condensed.

Particularly preferred electron-rich heteroaromatic ring systems R¹contain, as heteroaryl group, pyrrole, furan, thiophene, benzothiophene,benzofuran, indole, carbazole, dibenzothiophene, dibenzofuran and/orazacarbazole. The electron-rich heteroaromatic ring systems here are, inparticular, selected from the structures of the formulae (12) to (38)given above.

In an embodiment of the invention, preferences given above can becombined with one another as desired.

Examples of preferred compounds of the above-mentioned embodiments orcompounds as can preferably be employed in electronic devices are thecompounds of the following structures (1) to (91).

The compounds according to the invention can be prepared by syntheticsteps known to the person skilled in the art, as depicted schematicallyin Scheme 1 to 3.

A suitable synthetic method is the reaction of1,12-dilithiotriphenylene×2 TMEDA (Chanda et al., Organometallics 2007,26(7), 1635-1642) with electrophiles to give the compounds of theformula 1 to 3 according to the invention, as depicted in Scheme 1.

In addition, correspondingly substituted triphenylene derivatives can beconverted into aromatic or heteroaromatic hydrocarbons, amines, ethers,thioethers, etc., by methods of organic chemistry which are familiar tothe person skilled in the art, such as, for example, by Suzuki, Stille,Heck, Sonogashira, Yamamoto, Negishi, Ullmann or Buchwald couplings, asshown by way of example in Scheme 2. <Pd> here stands for a palladiumcatalyst.

In addition, correspondingly substituted triphenylene derivatives (Saitoet al., J. Organomet. Chem. 2010, 695(7), 1035-1041) can befunctionalised further in a plurality of steps, as shown by way ofexample in Scheme 3.

The present invention therefore furthermore relates to a process for thepreparation of a compound of the formula (1) or (2) by reaction of1,12-dilithiotriphenylene derivatives with electrophiles or by reactionof halogen- or amino-substituted triphenylene derivatives in ametal-catalysed coupling reaction.

The compounds according to the invention described above, in particularcompounds which are substituted by reactive leaving groups, such asbromine, iodine, chlorine, boronic acid or boronic acid ester, or byreactive, polymerisable groups, such as olefins or oxetanes, can be usedas monomers for the generation of corresponding oligomers, dendrimers orpolymers. The oligomerisation or polymerisation here preferably takesplace via the halogen functionality or the boronic acid functionality orvia the polymerisable group. It is furthermore possible to crosslink thepolymers via groups of this type. The compounds and polymers accordingto the invention can be employed as crosslinked or uncrosslinked layer.

The invention therefore furthermore relates to oligomers, polymers ordendrimers containing one or more of the compounds according to theinvention indicated above, where one or more bonds are present from thecompound according to the invention to the polymer, oligomer ordendrimer. Depending on the linking of the compound according to theinvention, this therefore forms a side chain of the oligomer or polymeror is linked in the main chain. The polymers, oligomers or dendrimersmay be conjugated, partially conjugated or non-conjugated. The oligomersor polymers may be linear, branched or dendritic. The same preferencesas described above apply to the recurring units of the compoundsaccording to the invention in oligomers, dendrimers and polymers.

For the preparation of the oligomers or polymers, the monomers accordingto the invention are homopolymerised or copolymerised with furthermonomers. Preference is given to homopolymers or copolymers in which theunits of the formula (1) or (2) or the preferred embodiments indicatedabove are present to the extent of 0.01 to 99.9 mol %, preferably 5 to90 mol %, particularly preferably 20 to 80 mol %. Suitable and preferredcomonomers which form the polymer backbone are selected from fluorenes(for example in accordance with EP 842208 or WO 2000/22026),spirobifluorenes (for example in accordance with EP 707020, EP 894107 orWO 2006/061181), para-phenylenes (for example in accordance with WO92/18552), carbazoles (for example in accordance with WO 2004/070772 orWO 2004/113468), thiophenes (for example in accordance with EP 1028136),dihydrophenanthrenes (for example in accordance with WO 2005/014689),cis- and trans-indenofluorenes (for example in accordance with WO2004/041901 or WO 2004/113412), ketones (for example in accordance withWO 2005/040302), phenanthrenes (for example in accordance with WO2005/104264 or WO 2007/017066) or also a plurality of these units. Thepolymers, oligomers and dendrimers may also contain further units, forexample hole-transport units, in particular those based ontriarylamines, and/or electron-transport units. In addition, thepolymers may contain phosphorescent emitters, either copolymerised ormixed in as a blend. In particular, the combination of units of theformula (1) or (2) or the preferred embodiments indicated above withphosphorescent emitters leads to particularly good results.

Furthermore, the compounds of the formula (1) or (2) or the preferredembodiments indicated above may also be functionalised further and thusconverted into extended structures. The reaction with arylboronic acidsby the Suzuki method or with primary or secondary amines by theHartwigBuchwald method may be mentioned here as an example. Thus, thecompounds of the formula (1) or (2) or the preferred embodimentsmentioned here may also be bonded directly to phosphorescent metalcomplexes or also to other metal complexes.

The compounds according to the invention are suitable for use in anelectronic device. An electronic device here is taken to mean a devicewhich comprises at least one layer which comprises at least one organiccompound. However, the component here may also comprise inorganicmaterials or also layers built up entirely from inorganic materials.

The present invention therefore furthermore relates to the use of theabove-mentioned compounds according to the invention in an electronicdevice, in particular in an organic electroluminescent device.

The present invention still furthermore relates to an electronic devicecomprising at least one of the above-mentioned compounds according tothe invention. The preferences stated above likewise apply to theelectronic devices.

The electronic device is preferably selected from the group consistingof organic electroluminescent devices (OLEDs), organic integratedcircuits (O-ICs), organic field-effect transistors (O-FETs), organicthin-film transistors (O-TFTs), organic light-emitting transistors(O-LETs), organic solar cells (O-SCs), organic optical detectors,organic photoreceptors, organic field-quench devices (O-FQDs),light-emitting electrochemical cells (LECs), organic laser diodes(O-lasers) and “organic plasmon emitting devices” (D. M. Koller et al.,Nature Photonics 2008, 1-4), but preferably organic electroluminescentdevices (OLEDs), particularly preferably phosphorescent OLEDs.

The organic electroluminescent device comprises cathode, anode and atleast one emitting layer. Apart from these layers, it may also comprisefurther layers, for example in each case one or more hole-injectionlayers, hole-transport layers, hole-blocking layers, electron-transportlayers, electron-injection layers, exciton-blocking layers,electron-blocking layers and/or charge-generation layers. It is likewisepossible for interlayers, which have, for example, an exciton-blockingfunction, to be introduced between two emitting layers. However, itshould be pointed out that each of these layers does not necessarilyhave to be present. The organic electroluminescent device here maycomprise one emitting layer or a plurality of emitting layers. If aplurality of emission layers are present, these preferably have in totala plurality of emission maxima between 380 nm and 750 nm, resultingoverall in white emission, i.e. various emitting compounds which areable to fluoresce or phosphoresce are used in the emitting layers.Particular preference is given to systems having three emitting layers,where the three layers exhibit blue, green and orange or red emission(for the basic structure see, for example, WO 2005/011013).

The compound according to the invention in accordance with theabove-mentioned embodiments can be employed in various layers, dependingon the precise structure. Preference is given to an organicelectroluminescent device comprising a compound of the formula (1) or(2) or the preferred embodiments indicated above as matrix material forfluorescent or phosphorescent emitters, in particular for phosphorescentemitters, and/or as fluorescent emitter and/or in a hole-blocking layerand/or in an electron-transport layer and/or in an electron-blocking orexciton-blocking layer and/or in a hole-transport or hole-injectionlayer, depending on the precise substitution. The preferred embodimentsindicated above also apply to the use of the materials in organicelectronic devices.

In a further embodiment of the invention, the organic electroluminescentdevice comprises the compound of the formula (1) or (2) or the preferredembodiments indicated above in an optical coupling-out layer. An opticalcoupling-out layer here is taken to mean a layer which is not locatedbetween the anode and the cathode, but instead which is applied to anelectrode outside the actual device, for example between an electrodeand a substrate, in order to improve the optical coupling-out.

In a preferred embodiment of the invention, the compound of the formula(1) or (2) or the preferred embodiments indicated above is employed asmatrix material for a fluorescent or phosphorescent compound, inparticular for a phosphorescent compound, in an emitting layer. Theorganic electroluminescent device here may comprise one emitting layeror a plurality of emitting layers, where at least one emitting layercomprises at least one compound according to the invention as matrixmaterial.

If the compound of the formula (1) or (2) or the preferred embodimentsindicated above is employed as matrix material for an emitting compoundin an emitting layer, it is preferably employed in combination with oneor more phosphorescent materials (triplet emitters). Phosphorescence inthe sense of this invention is taken to mean the luminescence from anexcited state of relatively high spin multiplicity, i.e. a spin state>1,in particular from an excited triplet state. For the purposes of thisapplication, all luminescent complexes with transition metals orlanthanides, in particular all iridium, platinum and copper complexes,are to be regarded as phosphorescent compounds.

The mixture of the compound of the formula (1) or (2) or the preferredembodiments indicated above and the emitting compound comprises between99 and 1% by vol., preferably between 98 and 10% by vol., particularlypreferably between 97 and 60% by vol., in particular between 95 and 80%by vol., of the compound of the formula (1) or (2) or the preferredembodiments indicated above, based on the entire mixture comprisingemitter and matrix material. Correspondingly, the mixture comprisesbetween 1 and 99% by vol., preferably between 2 and 90% by vol.,particularly preferably between 3 and 40% by vol., in particular between5 and 20% by vol., of the emitter, based on the entire mixturecomprising emitter and matrix material.

A further preferred embodiment of the present invention is the use ofthe compound of the formula (1) or (2) or the preferred embodimentsindicated above as matrix material for a phosphorescent emitter incombination with a further matrix material. Particularly suitable matrixmaterials which can be employed in combination with the compounds of theformula (1) or (2) or the preferred embodiments indicated above arearomatic ketones, aromatic phosphine oxides or aromatic sulfoxides orsulfones, for example in accordance with WO 2004/013080, WO 2004/093207,WO 2006/005627 or WO 2010/006680, triarylamines, carbazole derivatives,for example CBP (N,N-biscarbazolylbiphenyl) or the carbazole derivativesdisclosed in WO 2005/039246, US 2005/0069729, JP 2004/288381, EP 1205527or WO 2008/086851, indolocarbazole derivatives, for example inaccordance with WO 2007/063754 or WO 2008/056746, indenocarbazolederivatives, for example in accordance with WO 2010/136109 or WO2011/000455, azacarbazole derivatives, for example in accordance with EP1617710, EP 1617711, EP 1731584, JP 2005/347160, bipolar matrixmaterials, for example in accordance with WO 2007/137725, silanes, forexample in accordance with WO 2005/111172, azaboroles or boronic esters,for example in accordance with WO 2006/117052, triazine derivatives, forexample in accordance with WO 2007/063754, WO 2008/056746, WO2010/015306, WO 2011/057706, WO 2011/060859 or WO 2011/060877, zinccomplexes, for example in accordance with EP 652273 or WO 2009/062578,diazasilole or tetraazasilole derivatives, for example in accordancewith WO 2010/054729, diazaphosphole derivatives, for example inaccordance with WO 2010/054730, bridged carbazole derivatives, forexample in accordance with the unpublished applications WO 2011/042107or WO 2011/060867. A further phosphorescent emitter which emits atshorter wavelength than the actual emitter may likewise be present inthe mixture as co-host.

Suitable as phosphorescent compound (=triplet emitter) are, inparticular, compounds which emit light, preferably in the visibleregion, on suitable excitation and in addition contain at least one atomhaving an atomic number greater than 20, preferably greater than 38 andless than 84, particularly preferably greater than 56 and less than 80,in particular a metal having this atomic number. The phosphorescentemitters used are preferably compounds which contain copper, molybdenum,tungsten, rhenium, ruthenium, osmium, rhodium, iridium, palladium,platinum, silver, gold or europium, in particular compounds whichcontain iridium or platinum.

Examples of the emitters described above are revealed by theapplications WO 00/70655, WO 01/41512, WO 02/02714, WO 02/15645, EP1191613, EP 1191612, EP 1191614, WO 05/033244, WO 05/019373 and US2005/0258742. In general, all phosphorescent complexes as used inaccordance with the prior art for phosphorescent OLEDs and as are knownto the person skilled in the art in the area of organicelectroluminescence are suitable, and the person skilled in the art willbe able to use further phosphorescent complexes without inventive step.

Examples of suitable phosphorescent compounds are indicated in thefollowing table.

In a further embodiment of the invention, the organic electroluminescentdevice does not comprise a separate hole-injection layer and/orhole-transport layer and/or hole-blocking layer and/orelectron-transport layer, i.e. the emitting layer is directly adjacentto the hole-injection layer or the anode, and/or the emitting layer isdirectly adjacent to the electron-transport layer or theelectron-injection layer or the cathode, as described, for example, inWO 2005/053051. It is furthermore possible to use a metal complex whichis identical or similar to the metal complex in the emitting layer ashole-transport or hole-injection material directly adjacent to theemitting layer, as described, for example, in WO 2009/030981.

In a further preferred embodiment of the invention, the compound of theformula (1) or (2) or the preferred embodiments indicated above will beemployed as matrix material for a fluorescent emitter in an emittinglayer.

Suitable fluorescent dopants are selected, for example, from the groupof the monostyrylamines, the distyrylamines, the tristyrylamines, thetetrastyrylamines, the styrylphosphines, the styryl ethers and thearylamines. A monostyrylamine is taken to mean a compound which containsone substituted or unsubstituted styryl group and at least one,preferably aromatic, amine. A distyrylamine is taken to mean a compoundwhich contains two substituted or unsubstituted styryl groups and atleast one, preferably aromatic, amine. A tristyrylamine is taken to meana compound which contains three substituted or unsubstituted styrylgroups and at least one, preferably aromatic, amine. A tetrastyrylamineis taken to mean a compound which contains four substituted orunsubstituted styryl groups and at least one, preferably aromatic,amine. The styryl groups are particularly preferably stilbenes, whichmay also be further substituted. Corresponding phosphines and ethers aredefined analogously to the amines. An arylamine or aromatic amine in thesense of this invention is taken to mean a compound which contains threesubstituted or unsubstituted aromatic or heteroaromatic ring systemsbonded directly to the nitrogen. At least one of these aromatic orheteroaromatic ring systems is preferably a condensed ring system,particularly preferably having at least 14 aromatic ring atoms.Preferred examples thereof are aromatic anthracenamines, aromaticpyrenamines, aromatic pyrenediamines, aromatic chrysenamines or aromaticchrysenediamines. An aromatic anthracenamine is taken to mean a compoundin which a diarylamino group is bonded directly to an anthracene group,preferably in the 9-position or in the 2-position. Aromatic pyrenamines,pyrenediamines, chrysenamines and chrysenediamines are definedanalogously thereto, where the diarylamino groups on the pyrene arepreferably bonded in the 1-position or in the 1,6-position. Furtherpreferred dopants are selected from indenofluorenamines orindenofluorenediamines, for example in accordance with WO 2006/108497 orWO 2006/122630, benzoindenofluorenamines or benzoindenofluorenediamines,for example in accordance with WO 2008/006449, anddibenzoindenofluorenamines or dibenzoindenofluorenediamines, for examplein accordance with WO 2007/140847. Examples of dopants from the class ofthe styrylamines are substituted or unsubstituted tristilbenamines orthe dopants described in WO 2006/000388, WO 2006/058737, WO 2006/000389,WO 2007/065549 and WO 2007/115610. Furthermore suitable fluorescentdopants are the condensed hydrocarbons disclosed in WO 2010/012328.

In a further preferred embodiment of the invention, the compound of theformula (1) or (2) or the preferred embodiments indicated above will beemployed as fluorescent emitter in an emitting layer.

Suitable host materials (matrix materials) for the fluorescent dopants,in particular for the above-mentioned dopants, are selected, forexample, from the classes of the oligoarylenes (for example2,2′,7,7′-tetraphenylspirobifluorene in accordance with EP 676461 ordinaphthylanthracene), in particular the oligoarylenes containingcondensed aromatic groups, in particular anthracenes, theoligoarylenevinylenes (for example DPVBi or spiro-DPVBi in accordancewith EP 676461), the polypodal metal complexes (for example inaccordance with WO 2004/081017), the holeconducting compounds (forexample in accordance with WO 2004/058911), the electron-conductingcompounds, in particular ketones, phosphine oxides, sulfoxides, etc.(for example in accordance with WO 2005/084081 and WO 2005/084082), theatropisomers (for example in accordance with WO 2006/048268), theboronic acid derivatives (for example in accordance with WO2006/117052), the benzanthracene derivatives (for examplebenz[a]anthracene derivatives in accordance with WO 2008/145239 or WO2011/012212) and the benzophenanthrene derivatives (for examplebenz[c]phenanthrene derivatives in accordance with WO 2010/083869).Particularly preferred host materials are selected from the classes ofthe oligoarylenes, containing naphthalene, anthracene, benzanthracene,in particular benz[a]anthracene, benzophenanthrene, in particularbenz[c]phenanthrene, and/or pyrene, or atropisomers of these compounds.Very particularly preferred matrix materials for the fluorescent emitterare anthracene derivatives. An oligoarylene in the sense of thisinvention is intended to be taken to mean a compound in which at leastthree aryl or arylene groups are bonded to one another.

In a further preferred embodiment of the invention, the compound of theformula (1) or (2) or the preferred embodiments indicated above isemployed as electron-transport material in an electron-transport orelectron-injection layer. The emitting layer here may be fluorescent orphosphorescent. If the compound is employed as electron-transportmaterial, it may be preferred for it to be doped, for example withalkali-metal complexes, such as, for example, LiQ (lithiumhydroxyquinolinate).

In still a further preferred embodiment of the invention, the compoundof the formula (1) or (2) or the preferred embodiments indicated aboveis employed in a hole-blocking layer, in particular in a phosphorescentOLED. A hole-blocking layer is taken to mean a layer which is directlyadjacent to an emitting layer on the cathode side.

It is furthermore possible to use the compound of the formula (1) or (2)or the preferred embodiments indicated above both in a hole-blockinglayer or electron-transport layer and also as matrix in an emittinglayer.

In still a further embodiment of the invention, the compound of theformula (1) or (2) or the preferred embodiments indicated above isemployed in a hole-transport layer or in an electron-blocking layer orexciton-blocking layer.

In the further layers of the organic electroluminescent device accordingto the invention, it is possible to use all materials as usuallyemployed in accordance with the prior art. The person skilled in the artwill therefore be able, without inventive step, to employ all materialsknown for organic electroluminescent devices in combination with thecompounds of the formula (1) or (2) according to the invention or thepreferred embodiments indicated above.

Preference is furthermore given to an organic electroluminescent device,characterised in that one or more layers are coated by means of asublimation process, in which the materials are vapour-deposited invacuum sublimation units at an initial pressure of less than 10⁻⁵ mbar,preferably less than 10⁻⁶ mbar. However, it is also possible for theinitial pressure to be even lower, for example less than 10⁻⁷ mbar.

Preference is likewise given to an organic electroluminescent device,characterised in that one or more layers are coated by means of the OVPD(organic vapour phase deposition) process or with the aid of carrier-gassublimation, in which the materials are applied at a pressure between10⁻⁵ mbar and 1 bar. A special case of this process is the OVJP (organicvapour jet printing) process, in which the materials are applieddirectly through a nozzle and thus structured (for example M. S. Arnoldet al., Appl. Phys. Lett. 2008, 92, 053301).

Preference is furthermore given to an organic electroluminescent device,characterised in that one or more layers are produced from solution,such as, for example, by spin coating, or by means of any desiredprinting process, such as, for example, screen printing, flexographicprinting, offset printing, LITI (light induced thermal imaging, thermaltransfer printing), inkjet printing or nozzle printing. Solublecompounds, which are obtained, for example, by suitable substitution,are necessary for this purpose. These processes are also particularlysuitable for oligomers, dendrimers and polymers.

Furthermore possible are hybrid processes, in which, for example, one ormore layers are applied from solution and one or more further layers areapplied by vapour deposition. Thus, it is possible, for example, for theemitting layer to be applied from solution and for an electron-transportlayer to be applied to this layer by vacuum vapour deposition

These processes are generally known to the person skilled in the art andcan be applied by him without inventive step to organicelectroluminescent devices comprising the compounds according to theinvention.

For processing from solution, formulations, in particular solutions,suspensions or mini-emulsions, of the compounds according to theinvention are required. The present invention therefore furthermorerelates to formulations, in particular solutions, suspensions ormini-emulsions, comprising at least one compound according to theinvention and at least one solvent, in particular an organic solvent.

The compounds according to the invention and the organicelectroluminescent devices according to the invention are distinguishedby the following surprising advantages over the prior art:

-   1. The compounds according to the invention or compounds of the    formula (1) or (2) or the preferred embodiments indicated above,    employed as matrix material for fluorescent or phosphorescent    emitters, result in very high efficiencies and in long lifetimes.    This applies, in particular, if the compounds are employed as matrix    material for a phosphorescent emitter.-   2. The compounds according to the invention or compounds of the    formula (1) or (2) or the preferred embodiments indicated above are    suitable not only as matrix for red-phosphorescent compounds, but    also, in particular, for green-phosphorescent compounds.-   3. The compounds according to the invention are accessible    synthetically in a simple manner in few reaction steps and with high    yields.-   4. The compounds according to the invention, employed in organic    electroluminescent devices, result in high efficiencies and in steep    current/voltage curves with low use voltages.-   5. Also on use as electron-transport material or as hole-transport    material, the compounds according to the invention result in very    good properties with respect to the efficiency, lifetime and    operating voltage of organic electroluminescent devices.

These above-mentioned advantages are not accompanied by an impairment ofthe other electronic properties.

The invention is explained in greater detail by the following examples,without wishing to restrict it thereby. The person skilled in the artwill be able to carry out the invention throughout the range disclosedon the basis of the descriptions and prepare further compounds accordingto the invention without inventive step and use them in electronicdevices or use the process according to the invention.

EXAMPLES A) Synthesis Examples

The following syntheses are carried out, unless indicated otherwise, indried solvents under a protective-gas atmosphere. The metal complexesare additionally handled with exclusion of light. The solvents andreagents can be purchased, for example, from Sigma-ALDRICH or ABCR. TheCAS numbers of the starting materials are in each case indicated insquare brackets.

Example 14-(2,4,6-Trimethylphenyl)-4H-4-boracyclopenta[def]-triphenylene

A: 1,12-Dilithiotriphenylene*2 TMEDA

58.1 g (500 mmol) of N,N-tetramethylethylenediamine are added dropwiseto 312.5 ml (500 mmol) of n-butyllithium (1.6 M in n-hexane), and themixture is stirred at room temperature for 1 h. A solution of 22.8 g(100 mmol) of triphenylene in 150 ml of n-hexane is added dropwise tothe mixture, which is subsequently heated under reflux for 5 h. Afterabout 250 ml of n-hexane have been distilled off, the reaction mixtureis allowed to cool and is then cooled at −30° C. for 24 h, during whicha brown solid deposits. The brown solid is filtered off with suction,washed three times with 100 ml of ice-cold n-hexane each time and driedin vacuo. Yield: 134.7 g (285 mmol), 57%. Care:1,12-dilithiotriphenylene*2 TMEDA is pyrophoric!

B: 4-(2,4,6-Trimethylphenyl)-41′-4-boracyclopenta[def]tsriphenylene

A solution of 20.1 g (100 mmol) of dichloro-2,4,6-trimethylphenylborane[69464-76-2] in 500 ml of THF is added dropwise to a solution of 47.2 g(100 mmol) of 1,12-dilithiotriphenylene*2 TMEDA in 1500 ml of THF, andthe mixture is stirred at room temperature for 16 h. After removal ofthe solvent in vacuo, the residue is taken up in 500 ml ofdichloromethane and washed three times with 200 ml of water each time.After drying over sodium sulfate, the organic phase is evaporated, theresidue is recrystallised five times from dioxane and subsequentlysubjected to fractional sublimation in vacuo twice (p about 10⁻⁶ mbar, Tabout 300° C.). Yield 13.2 g (37 mmol), 37%. Purity: 99.9% according toHPLC.

The following compounds are accessible analogously by reaction of1,12-dilithiotriphenylene*2 TMEDA with the corresponding electrophiles:

Ex. Electrophile Product Yield 2

38% 3

32% 4

26% 5 SiCl₄ [10026-04-7]

14% 6

17% 7

41%

Example 81,10-Bis-(N-phenylcarbazol-2-yl)-4H-4-thiacyclopenta[def]-triphenylene

A) Triphenyleno[1,12-bcd]thiophene-2,11-diboronic acid

48.8 g (420 mmol) of N,N-tetramethylethylenediamine are added to asuspension of 25.8 g (100 mmol) of triphenyleno[1,12-bcd]thiophene[68558-73-6] in 2000 ml of n-hexane, and 250 ml (400 mmol) ofn-butyllithium (1.6 M in n-hexane) are then added dropwise, and themixture is subsequently stirred at 60° C. for 4 h. After the mixture hasbeen allowed to cool and cooled to −60° C., 46.8 g (450 mmol) oftrimethyl borate are added in one portion with vigorous stirring. Themixture is stirred at −60° C. for a further 30 min., then allowed towarm to room temperature, the n-hexane is removed in vacuo, the residueis taken up in 300 ml of THF, a mixture of 300 ml of water and 30 ml ofglacial acetic acid is added, the mixture is stirred for a further 2 h,the precipitated solid is filtered off with suction, washed twice with200 ml of water each time and dried in vacuo. Yield: 30.7 g. Purity:about 90.0% according to NMR, the crude product is subsequently usedwithout further purification.

B)1,10-Bis-(N-phenylcarbazol-2-yl)-4H-4-thiacyclopenta[def]-triphenylene

913 mg (3 mmol) of tri-o-tolylphosphine and then 112 mg (0.5 mmol) ofpalladium(II) acetate are added with stirring to a mixture of 17.3 g (50mmol) of triphenyleno[1,12-bcd]thiophene-2,11-diboronic acid, 41.9 g(130 mmol) of 2-bromo-9-phenylcarbazole [94994-62-4] and 31.8 g (150mmol) of tripotassium phosphate in a mixture of 200 ml of toluene, 100ml of ethanol and 300 ml of water, and the mixture is heated underreflux for 16 h. After cooling, the precipitated solid is filtered offwith suction, washed three times with 100 ml of a mixture of water andethanol (1:1, v:v) each time and then three times with 100 ml of ethanoleach time and dried in vacuo. The solid is subjected to hot-vapourextraction with toluene over aluminium oxide (basic, activity grade 1)five times and then subjected to fractional sublimation in vacuo twice(p about 10⁻⁶ mbar, T about 350° C.). Yield 12.6 g (34 mmol), 34%.Purity: 99.9% according to HPLC.

The following compounds are accessible analogously by reaction oftriphenyleno[1,12-bcd]thiophene-2,11-diboronic acid with thecorresponding bromides:

Ex. Bromide Product Yield  9

43% 10

31%

Example 11 4-Biphenyl-4-yl-4H-4-azacyclopenta[def]triphenylene

235 mg (1.3 mmol) of di-tert-butylchlorophosphine and then 225 g (1mmol) of palladium(II) acetate are added to a vigorously stirredsuspension of 12.1 g (50 mmol) of 4H-4-azacyclopenta[def]triphenylene[109606-75-9], 14.0 g (60 mmol) of 4-bromobiphenyl and 9.0 g (65 mmol)of potassium carbonate in 150 ml of toluene, and the mixture is heatedunder reflux for 16 h. After cooling to 60° C., water is added, themixture is stirred for a further 30 min., the precipitated solid is thenfiltered off with suction, washed three times with 100 ml of a mixtureof water and ethanol (1:1, v:v) each time and then three times with 100ml of ethanol each time and dried in vacuo. The solid is subjected tohot-vapour extraction with toluene over aluminium oxide (basic, activitygrade 1) five times and then subjected to fractional sublimation invacuo twice (p about 10⁻⁶ mbar, T about 320° C.). Yield: 7.3 g (19mmol), 37%. Purity: 99.9% according to HPLC.

The following compounds are accessible analogously by reaction4H-4-azacyclopenta[def]triphenylene with the corresponding bromides:

Ex. Bromide Product Yield 12

52% 13

44% 28

38% 29

41% 30

26% 31

35% 32

42% 33

33% 34

24% 35

28% 36

31% 37

40% 38

30% 39

22% 40

41% 41

44% 42

38% 43

22% 44

34% 45

19% 46

27%

Example 14 1,12-(Dibenzothiophen-2-yl)triphenylene

304 mg (1 mmol) of tri-o-tolylphosphine and then 45 mg (0.2 mmol) ofpalladium(II) acetate are added with stirring to a mixture of 9.6 g (20mmol) of 1,12-diiodotriphenylene [130197-34-1], 11.4 g (50 mmol) of2-dibenzothiopheneboronic acid [108847-24-1] and 10.6 g (50 mmol) oftripotassium phosphate in a mixture of 200 ml of toluene, 50 ml ofdioxane and 200 ml of water, and the mixture is heated under reflux for30 h. After cooling, the precipitated solid is filtered off withsuction, washed three times with 50 ml of a mixture of water and ethanol(1:1, v:v) each time and then three times with 50 ml of ethanol eachtime and dried in vacuo. The solid is subjected to hot-vapour extractionwith toluene over aluminium oxide (basic, activity grade 1) four timesand then subjected to fractional sublimation in vacuo twice (p about10⁻⁶ mbar, T about 310° C.). Yield 5.0 g (8.4 mmol), 42%. Purity: 99.9%according to HPLC.

The following compounds are accessible analogously by reaction with thecorresponding boronic acids:

Ex. Bromide Product Yield 47

13% 48

18%

Example 154,4-Bis[1,1′,3′,1″]terphenyl-5′-yl-4H-cyclopenta[def]-triphenylene

A solution of 48.7 g (100 mmol) ofbis[1,1′,3′,1″]terphenyl-5′-ylmethanone [1205748-29-3] in 500 ml of THFis added dropwise to a solution of 47.2 g (100 mmol) of1,12-dilithiotriphenylene*2 TMEDA in 1500 ml of THF, and the mixture isthen heated under reflux for 2 h. After quenching of the reactionmixture using 50 ml of ethanol and removal of the solvent in vacuo, theresidue is taken up in 500 ml of glacial acetic acid, 20 ml of conc.hydrochloric acid and 20 ml of acetic anhydride are added to thesuspension, and the mixture is heated under reflux for 3 h. Aftercooling, the precipitated solid is filtered off with suction, washedthree times with 100 ml of ethanol each time and dried in vacuo. Thesolid is recrystallised five times from DMF and subsequently subjectedto fractional sublimation in vacuo twice (p about 10⁻⁶ mbar, T about350° C.). Yield: 38.3 g (55 mmol), 55%. Purity: 99.9% according to HPLC.

Example 49 4,8,9,10-Pentaphenyl-4H-4-azacyclopenta[def]-triphenylene

A: 8,9-Diiodo-1,2,3,4-tetraphenyltriphenylene

7.6 ml (50 mmol) of N,N-tetramethylethylenediamine are added dropwise to31.3 ml (50 mmol) of n-butyllithium (1.6 M in n-hexane), and the mixtureis stirred at room temperature for 1 h. A solution of 10.6 g (20 mmol)of 1,2,3,4-tetraphenyltriphenylene [36262-81-4] in 50 ml of n-hexane isadded dropwise to the mixture, which is subsequently heated under refluxfor 5 h. After about 75 ml of n-hexane have been distilled off, thereaction mixture is allowed to cool, is cooled to −100° C., 50 ml of THFare added, and a solution of 7.0 g (55 mmol) of iodine in 50 ml of THFis then slowly added dropwise. When the addition is complete, themixture is allowed to warm slowly to room temperature. The reactionmixture is diluted with 200 ml of ethyl acetate, then washed once with100 ml of saturated sodium sulfite solution, twice with 100 ml of watereach time and once with 100 ml of sat. sodium chloride solution. Afterdrying over magnesium sulfate and removal of the solvent in vacuo, themixture is chromatographed on silica gel with heptane/ethyl acetate(4:1, v/v). Yield 7.1 g (9 mmol), 45%. Purity: 95% according to HPLC.

B:

A mixture of 7.8 g (10 mmol) of8,9-diiodo-1,2,3,4-tetraphenyltriphenylene, 1.0 ml (11 mmol) of aniline,2.4 g (25 mmol) of sodium tert-butoxide, 809 mg (4 mmol) oftri-tert-butylphosphine, 500 mg (2 mmol) of palladium(II) acetate and100 ml of toluene is heated under reflux for 16 h. After cooling, 100 mlof toluene are added to the reaction mixture, the mixture is washedtwice with 100 ml of water each time, dried over magnesium sulfate, andthe solvent is then removed in vacuo. The solid obtained in this way issubjected to hot-vapour extraction with toluene over aluminium oxide(basic, activity grade 1) four times and then subjected to fractionalsublimation in vacuo twice (p about 10⁻⁶ mbar, T about 370° C.). Yield2.9 g (4.6 mmol), 46%. Purity: 99.9% according to HPLC.

The following compounds are accessible analogously by reaction with thecorresponding amines:

Ex. Amine Product Yield 50

38% 51

30%

B) Device Examples Example 16 Production of OLEDs

OLEDs according to the invention and OLEDs in accordance with the priorart are produced by a general process in accordance with WO 2004/058911,which is adapted to the circumstances described here (layer-thicknessvariation, materials used).

The results for various OLEDs are presented in the following examples(see Tables 1, 2, 3, 4). Glass plates coated with structured ITO (indiumtin oxide) in a thickness of 150 nm are coated with 20 nm of PEDOT(poly(3,4-ethylenedioxy-2,5-thiophene), applied by spin coating fromwater; purchased from H. C. Starck, Goslar, Germany) for improvedprocessing. These coated glass plates form the substrates to which theOLEDs are applied. The OLEDs have in principle the following layerstructure: substrate/hole-injection layer (HIL, with HIL1, 20nm)/hole-transport layer (HTL, with HTM1 (reference) or the HTMsaccording to the invention, 20 nm)/electron-blocking layer, optional(EBL, 10 nm)/emission layer (EML with the individual matrices accordingto the invention or mixed matrices M, 40 nm)/electron-transport layer(ETL, with ETL1, 20 nm)/electron-injection layer (EIL, with LIF, 1 nm)and finally a cathode. The cathode is formed by an aluminium layer witha thickness of 100 nm. The precise structure of the OLEDs, in particularthe structure of the hole-conductor or emitter layer, and the resultsobtained with these OLEDs on use of the compounds according to theinvention as hole-conductor material, matrix materials forphosphorescent emitters, as matrix materials for fluorescent emittersand as fluorescent dopants is shown in Table 1, 2, 3 and 4.

The % data here relate to % by vol. The results for the use of compoundsaccording to the invention both as matrix materials for phosphorescentemitters and also as hole-transport materials are shown in Table 1, 2, 3and 4. Results for the use of compounds according to the invention bothas matrix materials for fluorescent emitters, as blue-fluorescentemitters and also as hole-transport materials are shown in Table 5.

The materials used for the production of the OLEDs are shown in Table 6.

All materials are applied by thermal vapour deposition in a vacuumchamber. The emission layer here always consists of at least one matrixmaterial (host material) and an emitting dopant (emitter), with whichthe matrix material or matrix materials is admixed in a certainproportion by volume by co-evaporation.

The as yet unoptimised OLEDs are characterised by standard methods. Forthis purpose, the electroluminescence spectra, the current efficiency(measured in cd/A) and the voltage are determined. The efficiencies andvoltages indicated in the tables relate to the corresponding values atan operating luminance of 1000 cd/m².

TABLE 1 Green-emitting OLEDs Efficiency Ex. EML [cd/A] Voltage [V] CIE,x/y 17 Ex. 1: 40.0 4.7 0.34/0.62 TEG1 (15%) 18 Ex. 2: 43.9 4.8 0.33/0.62TEG1 (15%) 19 Ex. 5: 51.0 4.6 0.33/0.62 TEG1 (10%) 20 Ex. 5: 54.7 4.50.32/0.61 TEG2 (15%) 21 Ex. 5 (60%): 55.4 4.2 0.32/0.61 EBL (25%): TEG2(15%) 22 Ex. 8: 28.0 4.1 0.33/0.61 TEG2 (15%) 23 Ex. 14: 45.2 4.20.32/0.61 TEG2 (15%)

TABLE 2 Green-emitting OLEDs without EBL Efficiency Ex. HTM/EML [cd/A]Voltage [V] CIE, x/y 17 Ex. 28/ 46.0 4.0 0.34/0.61 TMM1: TEG2 (10%) 52Ex. 29/ 57.9 3.8 0.35/0.61 TMM1: TEG2 (10%) 53 Ex. 37/ 67.0 3.90.35/0.61 TMM1: TEG2 (10%) 54 Ex. 29/ 64.5 3.7 0.35/0.61 TMM1 (60%) Ex.29 (33%) TEG2 (7%) 55 Ex. 29/ 66.1 3.8 0.35/0.61 TMM1 (60%) Ex. 37 (33%)TEG2 (7%) 56 Ex. 29/ 56.0 4.2 0.34/0.61 Ex. 30 (60%) Ex. 29 (33%) TEG2(7%) 57 Ex. 29/ 45.8 4.3 0.35/0.61 Ex. 31 (60%) Ex. 29 (33%) TEG2 (7%)58 Ex. 29/ 61.8 3.9 0.33/0.62 Ex. 32 (70%) Ex. 29 (25%) TEG1 (5%) 59 Ex.29/ 43.8 4.4 0.34/0.61 Ex. 33 (70%) Ex. 29 (25%) TEG2 (5%) 60 Ex. 29/48.9 4.2 0.35/0.61 Ex. 34 (60%) Ex. 29 (33%) TEG2 (7%) 61 Ex. 29/ 58.53.8 0.35/0.61 Ex. 35 (60%) Ex. 29 (30%) TEG2 (10%) 62 Ex. 29/ 61.6 3.80.35/0.61 Ex. 36 (65%) Ex. 29 (30%) TEG2 (5%) 63 Ex. 29/ 57.7 4.00.34/0.62 Ex. 38 (65%) Ex. 29 (30%) TEG2 (5%) 64 Ex. 37/ 45.2 4.10.35/0.61 Ex. 49 (50%) Ex. 29 (45%) TEG2 (5%) 65 Ex. 29/ 50.7 4.00.35/0.61 Ex. 50 (60%) Ex. 29 (33%) TEG2 (7%) 66 Ex. 29/ 49.3 4.20.35/0.61 Ex. 51 (70%) Ex. 29 (33%) TEG2 (7%)

TABLE 3 Red-emitting OLEDs Efficiency Ex. EML [cd/A] Voltage [V] CIE,x/y 24 Ex. 13: 12.4 4.8 0.67/0.33 TER1 (15%) 25 Ex. 11: (20%) 13.6 4.60.67/0.33 Ex. 15: (70%) TER2 (10%)

TABLE 4 Red-emitting OLEDs, without EBL Efficiency Ex. HTM/EML [cd/A]Voltage [V] CIE, x/y 26 Ex. 12/ 15.2 4.4 0.67/0.33 Ex. 8: TER1 (15%) 27Ex. 13/ 14.3 4.1 0.67/0.33 Ex. 13: TER2 (10%)

TABLE 5 Blue-emitting OLEDs Efficiency Ex. EML [cd/A] Voltage [V] CIE,x/y 67 Ex. 40: 5.3 6.5 0.14/0.15 SEB1 (5%) 68 Ex. 41: 5.2 6.4 0.14/0.15SEB1 (5%) 69 Ex. 42: 4.9 8.0 0.14/0.16 SEB2 (1%) 70 Ex. 43: 5.5 5.20.14/0.16 SEB2 (1%) 71 Ex. 44: 5.0 7.8 0.14/0.16 SEB2 (1%) 72 Ex. 42:4.0 6.0 0.15/0.18 Ex. 45 (5%) 73 Ex. 42: 6.2 5.8 0.15/0.16 Ex. 46 (5%)

TABLE 6 Structural formulae of the materials used

As is clearly evident from the examples given above, the materialsaccording to the invention are particularly suitable for use as matrixmaterials for phosphorescent emitters and as hole conductors, where theyresult in high efficiencies and low operating voltages.

1-15. (canceled)
 16. A neutral compound of the formula (1) or formula(2),

where the following applies to the symbols and indices used: X is oneach occurrence, identically or differently, BR², C(R²)₂, C═O, Si(R²)₂,Ge(R²)₂, Sn(R²)₂, NR², O, S, SO, SO₂, PR² or P(═O)R²; or X is, for n=0,a group of the following formula (3),

A is C, Si, Ge or Sn; the dashed bonds on A here indicate the bonding tothe triphenylene; Y is BR², O, S, NR², PR² or P(═O)R²; Z is on eachoccurrence, identically or differently, CR¹ or N, with the proviso thata maximum of two groups Z per ring stand for N; R is selected on eachoccurrence, identically or differently, from the group consisting ofN(Ar¹)₂, C(═O)Ar¹, P(═O)(Ar¹)₂ and an aromatic or heteroaromatic ringsystem having 5 to 60 aromatic ring atoms, which may in each case besubstituted by one or more radicals R¹; Ar¹ is on each occurrence,identically or differently, an aromatic or heteroaromatic ring systemhaving 5 to 60 aromatic ring atoms, which is optionally substituted byone or more non-aromatic radicals R³; two radicals Ar¹ here which arebonded to the same N atom or P atom may also be bridged to one anotherby a single bond or a bridge selected from N(R⁴), C(R⁴)₂, O or S; R¹ isselected on each occurrence, identically or differently, from the groupconsisting of H, D, F, Cl, Br, I, CN, NO₂, N(Ar¹)₂, N(R³)₂, C(═O)Ar¹,C(═O)R³, P(═O)(Ar¹)₂, a straight-chain alkyl, alkoxy or thioalkyl grouphaving 1 to 40 C atoms or a branched or cyclic alkyl, alkoxy orthioalkyl group having 3 to 40 C atoms or an alkenyl or alkynyl grouphaving 2 to 40 C atoms, where the alkyl, alkoxy, thioalkyl, alkenyl oralkynyl group is optionally substituted by one or more radicals R³ andwhere one or more non-adjacent CH₂ groups is optionally replaced byR³C═CR³, C≡C, Si(R³)₂, Ge(R³)₂, Sn(R³)₂, C═O, C═S, C═Se, C═NR³,P(═O)(R³), SO, SO₂, NR³, O, S or CONR³ and where one or more H atoms isoptionally replaced by D, F, Cl, Br, I, CN or NO₂, an aromatic orheteroaromatic ring system having 5 to 60 aromatic ring atoms, which mayin each case be substituted by one or more radicals R³, an aryloxy orheteroaryloxy group having 5 to 60 aromatic ring atoms, which isoptionally substituted by one or more radicals R³, or a combination ofthese systems, where two or more adjacent substituents R¹ which arebonded to the same benzene ring may optionally form a monocyclic orpolycyclic, aliphatic, aromatic or heteroaromatic ring system; R² isselected on each occurrence, identically or differently, from the groupconsisting of a straight-chain alkyl group having 1 to 20 C atoms or abranched or cyclic alkyl group having 3 to 20 C atoms, each of which isoptionally substituted by one or more radicals R³, where one or morenon-adjacent CH₂ groups is optionally replaced by R³C═CR³, CC, Si(R³)₂,C═O, C═NR³, P(═O)(R³), SO, SO₂, NR³, O, S or CONR³ and where one or moreH atoms is optionally replaced by D, F, Cl, Br, I, CN or NO₂, or anaromatic or heteroaromatic ring system having 5 to 60 aromatic ringatoms, which may in each case be substituted by one or more radicals R³,where two substituents R² which are bonded to the same carbon, silicon,germanium or tin atom may optionally form a monocyclic or polycyclic,aliphatic, aromatic or heteroaromatic ring system with one another,which is optionally substituted by one or more radicals R³; R³ isselected on each occurrence, identically or differently, from the groupconsisting of H, D, F, Cl, Br, I, CN, NO₂, N(R⁴)₂, C(═O)Ar¹, C(═O)R⁴,P(═O)(Ar¹)₂, a straight-chain alkyl, alkoxy or thioalkyl group having 1to 40 C atoms or a branched or cyclic alkyl, alkoxy or thioalkyl grouphaving 3 to 40 C atoms or an alkenyl or alkynyl group having 2 to 40 Catoms, where the alkyl, alkoxy, thioalkyl, alkenyl or alkynyl group isoptionally substituted by one or more radicals R⁴, where one or morenon-adjacent CH₂ groups is optionally replaced by R⁴C═CR⁴, C≡C, Si(R⁴)₂,C═O, C═NR⁴, P(═O)(R⁴), SO, SO₂, NR⁴, O, S or CONR⁴ and where one or moreH atoms is optionally replaced by D, F, Cl, Br, I, CN or NO₂, anaromatic or heteroaromatic ring system having 5 to 60 aromatic ringatoms, which may in each case be substituted by one or more radicals R⁴,an aryloxy or heteroaryloxy group having 5 to 60 aromatic ring atoms,which is optionally substituted by one or more radicals R⁴, or acombination of these systems, where two or more adjacent substituents R³may optionally form a monocyclic or polycyclic, aliphatic, aromatic orheteroaromatic ring system, which is optionally substituted by one ormore radicals R⁴; R⁴ is selected from the group consisting of H, D, F,CN, an aliphatic hydrocarbon radical having 1 to 20 C atoms, an aromaticor heteroaromatic ring system having 5 to 30 aromatic ring atoms, inwhich one or more H atoms is optionally replaced by D, F, Cl, Br, I, CNor an alkyl group having 1 to 5 C atoms, where two or more adjacentsubstituents R⁴ may form a mono- or polycyclic, aliphatic, aromatic orheteroaromatic ring system with one another; n is 0 or 1; with theproviso that at least one group R¹ in formula (1) stands for an aromaticor heteroaromatic ring system if X stands for C═O, O, S, SO or SO₂ andn=0; and furthermore with the proviso that the following compounds areexcluded from the invention:


17. The compound according to claim 16, wherein the compound is selectedfrom the compounds of the formulae (4) to (7),

where the symbols used have the meanings given in claim
 16. 18. Thecompound according to claim 16, wherein the compound is selected fromthe compounds of the formulae (4a) to (7a),

where the symbols used have the meanings given in claim
 16. 19. Thecompound according claim 16, wherein, in compounds of the formula (1)where n=0 or in compounds of the formula (4) or formula (4a), X isselected from the group consisting of C(R²)₂, Si(R²)₂ and N(R²) and R²stands, identically or differently on each occurrence, for an aromaticor heteroaromatic ring system having 5 to 40 aromatic ring atoms, whichmay in each case also be substituted by one or more radicals R³ andwhere two radicals R² may also form an aromatic ring system with oneanother; and in that, in compounds of the formula (1) where X=formula(3) or in compounds of the formula (5) or formula (5a), the twotriphenylene moieties which are bonded to A are in each case substitutedidentically and A stands for carbon or silicon; and in that, incompounds of the formula (1) where n=1 or in compounds of the formula(6) or formula (6a), the group X—Y—X is selected from the groupconsisting of C(R²)₂—O—C(R²)₂, Si(R²)₂—O—Si(R²)₂, O—BR²—O, O—PR²—O,O—P(═O)R²—O and C(═O)—NR²—C(═O); and in that, in compounds of theformula (2) or (7) or (7a), the two radicals R are identical.
 20. Aprocess for the preparation of the compound according to claim 16 whichcomprises reacting 1,12-dilithiotriphenylene derivatives withelectrophiles or by reaction of halogen- or amino-substitutedtriphenylene derivatives in a metal-catalyzed coupling reaction.
 21. Anoligomer, polymer or dendrimer containing one or more of the compoundsaccording to claim 16, where one or more bonds are present from thecompound to the polymer, oligomer or dendrimer.
 22. An electronic devicewhich comprises the compound according to claim
 16. 23. An electronicdevice which comprises the oligomer, polymer or dendrimer according toclaim
 21. 24. The electronic device as claimed in claim 22, wherein thedevice is selected from the group consisting of organicelectroluminescent devices (OLEDs), organic integrated circuits (O-ICs),organic field-effect transistors (O-FETs), organic thin-film transistors(O-TFTs), organic light-emitting transistors (O-LETs), organic solarcells (O-SCs), organic optical detectors, organic photoreceptors,organic field-quench devices (O-FQDs), light-emitting electrochemicalcells (LECs), organic laser diodes (O-lasers) and organic plasmonemitting devices.
 25. An organic electroluminescent device whichcomprises the compound according to claim 16 is employed as matrixmaterial for fluorescent or phosphorescent emitters and/or asfluorescent emitter and/or in a hole-blocking layer and/or in anelectron-transport layer and/or in an electron-blocking orexciton-blocking layer and/or in a hole-transport or hole-injectionlayer and/or in an optical coupling-out layer.
 26. An organicelectroluminescent device which comprises the compound according toclaim 16 is used as matrix material for phosphorescent emitters and inthat at least one radical R1 stands for N(Ar1)2, C(═O)Ar1, P(═O)(Ar1)2or for an aromatic or heteroaromatic ring system having 5 to 60 aromaticring atoms, which is optionally substituted by one or more radicals R3,where the group Ar1 or the radicals on Ar1 or the aromatic orheteroaromatic ring system or the radicals R3 on the aromatic orheteroaromatic ring system contains no condensed aryl groups having morethan 10 C atoms and no condensed heteroaryl groups in which more thantwo aryl or 6-membered heteroaryl groups are condensed directly onto oneanother; and/or in that, in the compound of the formula (2) or formula(7) or formula (7a), R stands, identically or differently on eachoccurrence, for N(Ar¹)₂, C(═O)Ar¹, P(═O)(Ar¹)₂ or an aromatic orheteroaromatic ring system having 5 to 60 aromatic ring atoms, which isoptionally substituted by one or more radicals R¹, where the group Ar¹or the radicals on Ar¹ or the aromatic or heteroaromatic ring system orthe radicals R¹ on the aromatic or heteroaromatic ring system containsno condensed aryl groups having more than 10 C atoms and no condensedheteroaryl groups in which more than two aryl or 6-membered heteroarylgroups are condensed directly onto one another.
 27. The organicelectroluminescent device according to claim 26, wherein at least oneradical R¹ and/or R² and/or R is selected from the group consisting ofphenyl, ortho-, meta- or para-biphenyl, ortho-, meta- or para-terphenyl,ortho-, meta-, para- or branched quaterphenyl, fluorene orspirobifluorene, each of which is optionally substituted by one or moreradicals R³, and/or in that at least one radical R¹ and/or R² and/or Ris selected from the structures of the formulae (8) to (38),

where wherein R³ is selected on each occurrence, identically ordifferently, from the group consisting of H, D, F, Cl, Br, I, CN, NO₂,N(R⁴)₂, C(═O)Ar¹, C(═O)R⁴, P(═O)(Ar¹)₂, a straight-chain alkyl, alkoxyor thioalkyl group having 1 to 40 C atoms or a branched or cyclic alkyl,alkoxy or thioalkyl group having 3 to 40 C atoms or an alkenyl oralkynyl group having 2 to 40 C atoms, where the alkyl, alkoxy,thioalkyl, alkenyl or alkynyl group is optionally substituted by one ormore radicals R⁴, where one or more non-adjacent CH₂ groups isoptionally replaced by R⁴C═CR⁴, CC, Si(R⁴)₂, C═O, C═NR⁴, P(═O)(R⁴), SO,SO₂, NR⁴, O, S or CONR⁴ and where one or more H atoms is optionallyreplaced by D, F, Cl, Br, I, CN or NO₂, an aromatic or heteroaromaticring system having 5 to 60 aromatic ring atoms, which may in each casebe substituted by one or more radicals R⁴, an aryloxy or heteroaryloxygroup having 5 to 60 aromatic ring atoms, which is optionallysubstituted by one or more radicals R⁴, or a combination of thesesystems, where two or more adjacent substituents R³ may optionally forma monocyclic or polycyclic, aliphatic, aromatic or heteroaromatic ringsystem, which is optionally substituted by one or more radicals R⁴; R⁴is selected from the group consisting of H, D, F, CN, an aliphatichydrocarbon radical having 1 to 20 C atoms, an aromatic orheteroaromatic ring system having 5 to 30 aromatic ring atoms, in whichone or more H atoms is optionally replaced by D, F, Cl, Br, I, CN or analkyl group having 1 to 5 C atoms, where two or more adjacentsubstituents R⁴ may form a mono- or polycyclic, aliphatic, aromatic orheteroaromatic ring system with one another; Ar¹ is on each occurrence,identically or differently, an aromatic or heteroaromatic ring systemhaving 5 to 60 aromatic ring atoms, which is optionally substituted byone or more non-aromatic radicals R³; two radicals Ar¹ here which arebonded to the same N atom or P atom may also be bridged to one anotherby a single bond or a bridge selected from N(R⁴), C(R⁴)₂, O or S; andthe dashed bond represents the bond to the triphenylene skeleton or toX; and/or in that at least one radical R¹ and/or R selected from thestructures of the formulae (39) to (41) and/or in that at least oneradical R² is selected from the structures of the formula (40),

Ar² is, identically or differently on each occurrence, an aromatic orheteroaromatic ring system having 5 to 24 aromatic ring atoms, which isoptionally substituted by one or more radicals R³; the sum of thearomatic ring atoms of all groups Ar² together is not greater than 60;and E is selected from the group consisting of C(R⁴)₂, NR⁴, O or S. 28.An organic electroluminescent device which comprises the compoundaccording to claim 16 is used as electron-transport material and atleast one radical R¹ and/or R stands for C(═O)Ar¹, P(═O)(Ar¹)₂ or for anelectron-deficient heteroaromatic ring system having 5 to 40 aromaticring atoms, which is optionally substituted by one or more radicals R³;and/or X stands for BR², C═O, SO, SO₂ or P(═O)(R²)₂.
 29. The organicelectroluminescent device according to claim 28, wherein theelectron-deficient heteroaromatic ring system R¹ and/or R² and/or Rcontains, as heteroaryl group, triazine, pyrimidine, pyrazine,pyridazine, pyridine, imidazole, pyrazole, oxazole, oxadiazole,triazole, thiazole, thiadiazole, benzimidazole, quinoline, isoquinolineor quinoxaline and in particular is selected from the structures of theformulae (8) to (11) according to claim 26 or from the formulae (42) to(45),

R³ is selected on each occurrence, identically or differently, from thegroup consisting of H, D, F, Cl, Br, I, CN, NO₂, N(R⁴)₂, C(═O)Ar¹,C(═O)R⁴, P(═O)(Ar¹)₂, a straight-chain alkyl, alkoxy or thioalkyl grouphaving 1 to 40 C atoms or a branched or cyclic alkyl, alkoxy orthioalkyl group having 3 to 40 C atoms or an alkenyl or alkynyl grouphaving 2 to 40 C atoms, where the alkyl, alkoxy, thioalkyl, alkenyl oralkynyl group is optionally substituted by one or more radicals R⁴,where one or more non-adjacent CH₂ groups is optionally replaced byR⁴C═CR⁴, CC, Si(R⁴)₂, C═O, C═NR⁴, P(═O)(R⁴), SO, SO₂, NR⁴, O, S or CONR⁴and where one or more H atoms is optionally replaced by D, F, Cl, Br, I,CN or NO₂, an aromatic or heteroaromatic ring system having 5 to 60aromatic ring atoms, which may in each case be substituted by one ormore radicals R⁴, an aryloxy or heteroaryloxy group having 5 to 60aromatic ring atoms, which is optionally substituted by one or moreradicals R⁴, or a combination of these systems, where two or moreadjacent substituents R³ may optionally form a monocyclic or polycyclic,aliphatic, aromatic or heteroaromatic ring system, which is optionallysubstituted by one or more radicals R⁴; R⁴ is selected from the groupconsisting of H, D, F, CN, an aliphatic hydrocarbon radical having 1 to20 C atoms, an aromatic or heteroaromatic ring system having 5 to 30aromatic ring atoms, in which one or more H atoms is optionally replacedby D, F, Cl, Br, I, CN or an alkyl group having 1 to 5 C atoms, wheretwo or more adjacent substituents R⁴ may form a mono- or polycyclic,aliphatic, aromatic or heteroaromatic ring system with one another; Ar¹is on each occurrence, identically or differently, an aromatic orheteroaromatic ring system having 5 to 60 aromatic ring atoms, which isoptionally substituted by one or more non-aromatic radicals R³; tworadicals Ar¹ here which are bonded to the same N atom or P atom may alsobe bridged to one another by a single bond or a bridge selected fromN(R⁴), C(R⁴)₂, O or S; and the dashed bond represents the bond to thetriphenylene skeleton or to X.
 30. An organic electroluminescent devicewhich comprises the compound according to claim 16 is used ashole-transport material or as emitting compound and at least one radicalR¹ and/or R stands for N(Ar¹)₂, for a triarylamino group or for anelectron-rich heteroaromatic ring system having 5 to 40 aromatic ringatoms, which is optionally substituted by one or more radicals R³;and/or X stands for NR² or PR².
 31. A formulation comprising at leastone compound according to claim 16 and at least one solvent.
 32. Aformulation comprising at least one or more polymers, oligomers ordendrimers according to claim 21 and at least one solvent.